CN110938291A - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract
The invention relates to a polylactic acid composite material and a preparation method thereof, wherein the polylactic acid composite material comprises the following raw materials in parts by weight: 100 parts of polylactic acid and 5-25 parts of elastomer; the elastomer is mainly prepared by reacting and extruding polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide; in the preparation of the elastomer, the feeding ratio of polylactic acid to acid lignin is 100 g: (8-20) g. The dicumyl peroxide is used as an initiator to initiate maleic anhydride to simultaneously react with polylactic acid and acid lignin to form an interpenetrating network elastomer, the main material is polylactic acid, and the polylactic acid composite material has good compatibility with the polylactic acid when used for preparing modified polylactic acid, has excellent impact resistance, thermal stability and ultraviolet degradation resistance, and also maintains excellent biodegradability.
Description
Technical Field
The invention relates to the field of composite materials, and particularly relates to a polylactic acid composite material and a preparation method thereof.
Background
The application of the traditional non-degradable plastics brings convenience to the production and the life of human beings, and brings hazards such as soil pollution, water body pollution and the like. With the gradual increase of the environmental protection consciousness of human beings, the craving for degradable environment-friendly materials is stronger and stronger. Polylactic acid (PLLA) is a biodegradable composite material with wide application prospect, the raw material of the PLLA is starch with wide sources, but the application of the PLLA is greatly limited due to the defect of poor impact resistance. In order to further expand the application field of PLLA, especially to meet the demand of the field with high requirement on the impact resistance of the material, researchers have made many researches and researches on improving the impact resistance of PLLA, and at present, the impact resistance is improved mainly by adding a toughening agent or a plasticizer to PLLA resin, however, the traditional toughening agent or plasticizer has poor compatibility with polylactic acid, and the plasticizer is precipitated in the use process of the PLLA material, so that the physical property, the mechanical property, the heat resistance and the service life of the polylactic acid are reduced, the biodegradability of the polylactic acid is influenced, and the cost is high, and the large-scale application is not facilitated.
Disclosure of Invention
Based on the above, the invention provides a polylactic acid composite material with better impact resistance, ultraviolet degradation resistance and biodegradability and a preparation method thereof.
The technical scheme of the invention is as follows.
The invention provides a polylactic acid composite material, which comprises the following raw materials in parts by weight: 100 parts of polylactic acid and 5-25 parts of elastomer;
the elastomer is mainly prepared by reacting and extruding polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide;
in the raw materials for preparing the elastomer, the feeding ratio of the polylactic acid to the acid lignin is 100 g: (8-20) g.
The polylactic acid composite material is prepared from 100 parts by mass of the polylactic acid and 10-20 parts by mass of the elastomer.
In the raw material for preparing the elastomer, the dosage of the dicumyl peroxide is 0.5 to 1.5 weight percent of the total amount of the polylactic acid and the acid lignin.
In the preparation of the elastomer, the amount of the maleic anhydride is 1.5 to 4 wt% of the total amount of the polylactic acid and the acid lignin.
In the raw materials for preparing the elastomer, the feeding ratio of the polylactic acid to the acid lignin is as follows: 100 g: (10-18) g.
In the polylactic acid composite material, the particle size of the elastomer is controlled to be less than 2mm through crushing.
In the polylactic acid composite material, the acid lignin is prepared by extracting orange straws with acid.
Another aspect of the present invention provides a method for preparing the above polylactic acid composite material, comprising the following steps:
mixing polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide to obtain a first premix;
reacting and extruding the first premix to prepare an elastomer;
mixing the elastomer and polylactic acid to obtain a second premix;
and melting and extruding the second premix to obtain the polylactic acid composite material.
In the preparation method, the melt extrusion is carried out by adopting a screw extruder, wherein the temperature of the screw extruder is as follows according to the advancing direction of the materials: 120-145 ℃, 135-155 ℃, 145-165 ℃, 155-175 ℃, 165-180 ℃ and the head temperature is 160-170 ℃.
In the above production method, the rotation speed of the screw extruder is 90 to 120 rpm.
Advantageous effects
The polylactic acid composite material is prepared by compounding polylactic acid through an elastomer, wherein the elastomer is prepared by reacting and extruding the polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide, the dicumyl peroxide is used as an initiator to initiate the reaction of the maleic anhydride with the acid lignin and the polylactic acid, and the prepared elastomer is an interpenetrating network elastomer formed by crosslinking the acid lignin and the polylactic acid. And the main material of the elastomer is polylactic acid, so that the elastomer has good compatibility with polylactic acid when used for preparing a polylactic acid composite material, and the prepared polylactic acid composite material also keeps excellent biodegradability. The acid lignin in the elastomer is a three-dimensional network high molecular compound of polyphenols, the basic structural unit of the acid lignin is a phenylpropane structure, the acid lignin containing a rigid benzene ring is introduced into the elastomer, the ultraviolet degradation resistance of the polylactic acid can be improved, the water absorption of the acid lignin is low, the degradation caused by the influence of external illumination and moisture in the using process can be reduced, and the service life of the material can be prolonged. The polylactic acid composite material can be prepared by mixing materials and extruding the materials by a screw extruder, the process is simple, and the sources of polylactic acid and acid lignin are rich, wherein the acid lignin can be extracted from straws of crops by acid, so that the production cost can be reduced, and the green cyclic utilization of resources can be promoted.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a polylactic acid composite material, which comprises the following raw materials in parts by weight: 100 parts of polylactic acid and 5-25 parts of elastomer.
The elastomer is mainly prepared by reacting and extruding polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide.
Wherein, in the preparation of the elastomer, the feeding ratio of the polylactic acid to the acid lignin is 100 g: (8-20) g.
The polylactic acid composite material compounds polylactic acid through the elastomer, wherein the elastomer is prepared by the reaction and extrusion of polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide, dicumyl peroxide is used as an initiator to initiate the reaction of the maleic anhydride with the acid lignin and the polylactic acid, the prepared elastomer is an interpenetrating network elastomer formed by crosslinking the acid lignin and the polylactic acid, the elastomer has a large molecular free space, and when the elastomer is acted by external force, the elastomer consumes stress through large deformation, so that the impact resistance of the polylactic acid base material can be greatly improved. And the main material of the elastomer is polylactic acid, so that the elastomer has good compatibility with polylactic acid when used for preparing a polylactic acid composite material, and the prepared polylactic acid composite material also keeps excellent biodegradability. The acid lignin in the elastomer is a three-dimensional network high molecular compound of polyphenols, the basic structural unit of the acid lignin is a phenylpropane structure, the acid lignin containing a rigid benzene ring is introduced into the elastomer, the ultraviolet degradation resistance of the polylactic acid can be improved, the water absorption of the acid lignin is low, the degradation caused by the influence of external illumination and moisture in the using process can be reduced, and the service life of the material can be prolonged.
In one embodiment, the polylactic acid composite material comprises 100 parts by mass of polylactic acid and 10-20 parts by mass of elastomer.
In one embodiment, the ratio of polylactic acid to acid lignin in the raw material for preparing the elastomer is as follows: 100 g: (10 g-18 g).
In one embodiment, the dicumyl peroxide is used in an amount of 0.5 wt% to 1.5 wt% of the total amount of the polylactic acid and the acid lignin in the raw material for preparing the elastomer.
Further, the amount of the maleic anhydride is 1.5 wt% -4 wt% of the total amount of the polylactic acid and the acid lignin.
Dicumyl peroxide is used as an initiator to initiate the reaction of maleic anhydride with acid lignin and polylactic acid.
The maleic anhydride reacts with the acid lignin and the polylactic acid at the same time, so that the acid lignin and the polylactic acid are crosslinked to form the elastomer with an interpenetrating network structure. This elastomer has very big molecule free space, and when receiving the exogenic action, the elastomer is through taking place big deformation consumption stress, but also can prevent the silver line to enlarge and increase through the deformation of self and shear zone, avoids weak position stress concentration and output crackle to can greatly improve polylactic acid substrate's shock resistance.
In one embodiment, the particle size of the elastomer is controlled to be less than 2mm by crushing. The smaller the size of the elastomer is, the larger the specific surface area is, so that the contact surface with the polylactic acid substrate can be increased, and the compatibility with the polylactic acid substrate is further improved.
It will be appreciated that the crushing may be carried out using a crusher, or other apparatus capable of effecting crushing of material.
In the polylactic acid composite material, the acid lignin is lignin extracted from the straws by acid.
The source of the acid lignin is rich, wherein the straws of the crops contain rich lignin, and the acid lignin can be extracted from the straws of the crops by using acid, so that the production cost can be reduced, and the green cyclic utilization of resources can be promoted.
An embodiment of the present invention further provides a method for preparing the polylactic acid composite material, including the following steps S10-S40.
S10, mixing polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide to obtain a first premix.
In one embodiment, the mixing is performed in a high speed mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
S20, reacting and extruding the first premix obtained in the step S10 to obtain the elastomer.
In one embodiment, the reactive extrusion is performed by using a screw extruder, wherein the temperature of the screw extruder is, in the material advancing direction, in sequence: 115-125 ℃, 120-140 ℃, 135-160 ℃, 150-170 ℃ and 160-175 ℃, and the head temperature is 160-170 ℃, and further, the rotating speed of the screw extruder is 80-110 rpm.
In the reaction extrusion process, the materials are subjected to a gradual temperature rise process, and under the initiation of dicumyl peroxide, maleic anhydride is fully reacted with polylactic acid and thermoplastic starch at the same time to form the interpenetrating network elastomer.
In one embodiment, step S20 further includes crushing the elastomer to a particle size of less than 2 mm.
It will be appreciated that the crushing may be carried out using a crusher, or other apparatus capable of effecting crushing of material.
S30, mixing the elastomer obtained in the step S20 and polylactic acid to obtain a second premix.
In one embodiment, the elastomer, polylactic acid, is mixed in a high speed mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
And S40, carrying out melt extrusion on the second premix obtained in the step S30 to obtain the polylactic acid composite material.
In one embodiment, the melt extrusion is performed by using a screw extruder, wherein the temperature of the screw extruder is, in order of the material advancing direction: 120-145 ℃, 135-155 ℃, 145-165 ℃, 155-175 ℃ and 165-180 ℃, the head temperature is 160-170 ℃, and further, the rotating speed of the screw extruder is 90-120 rpm.
The preparation method can prepare the polylactic acid composite material with better impact resistance, ultraviolet degradation resistance and biodegradability by mixing the materials and extruding the materials by a screw extruder, has simple process and rich sources of polylactic acid and acid lignin, wherein the acid lignin can be extracted from waste straws of crops by acid, and the prepared polylactic acid composite material can be biodegraded into carbon dioxide and water, thereby reducing the production cost and promoting the green recycling of resources.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The polylactic acid composite material and the method for preparing the same according to the present invention are exemplified herein, but the present invention is not limited to the following examples.
The preparation steps of the polylactic acid composite materials of the examples 1 to 6 and the comparative examples 1 to 3 are as follows:
1) weighing polylactic acid, acid lignin (or alkali lignin), maleic anhydride and dicumyl peroxide according to the table 1, adding into a high-speed mixer, mixing to obtain a premix, and using in the step 2).
2) And extruding the premix through a double-screw extruder, wherein the temperature of the double-screw extruder is as follows according to the advancing direction of the materials: 115 ℃ in the first zone, 135 ℃ in the second zone, 145 ℃ in the third zone, 160 ℃ in the fourth zone, 170 ℃ in the fifth zone, 165 ℃ in the head and 110rpm in the double-screw extruder) to obtain an elastomer, crushing the elastomer in a crusher, controlling the size of the elastomer to be less than 2mm, and preparing for use in step 3).
3) Weighing polylactic acid and elastomer according to the table 2, adding the polylactic acid and the elastomer into a high-speed mixer, mixing to obtain a primary mixed material, and using the primary mixed material in the step 4).
4) And melting and extruding the initial mixed material through a double-screw extruder (the temperature of the double-screw extruder is as follows according to the advancing direction of the material: 120 ℃ in the first zone, 140 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 175 ℃ in the fifth zone, 170 ℃ in the head and 100rpm in the double-screw extruder) to obtain the polylactic acid composite material.
TABLE 1
TABLE 2
Comparative example 4
The raw materials and the proportions of the raw materials in comparative example 4 are the same as those in example 3, except that in comparative example 1, all the raw materials are mixed and then directly melt-extruded, namely 897.7g of polylactic acid, 15g of acid lignin, 3.5g of maleic anhydride and 1.15g of dicumyl peroxide are added into a high-speed mixer and uniformly mixed to obtain a premix; and (3) melting and extruding the initial mixture by a double-screw extruder (the temperature of the double-screw extruder is 120 ℃ in the first zone, 140 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 175 ℃ in the fifth zone and 170 ℃ in the head according to the advancing direction of the materials, and the rotating speed of the double-screw extruder is 100rpm), so as to obtain the polylactic acid composite material.
Performance testing
1) And the modified polylactic acid and the raw material polylactic acid prepared in the examples 1 to 6 and the comparative examples 1 to 4 are subjected to an impact resistance test: performed according to standard GB1943-2007, the results are shown in table 3.
2) Modified polylactic acids obtained in examples 1 to 6 and comparative examples 1 to 4 and starting polylactic acid were subjected to Thermogravimetric Analysis (TGA) under an oxygen atmosphere at a temperature rise rate of 5 ℃/min, respectively, to Thermogravimetric weight loss tests, with 5% of polymer weight loss as an initial decomposition temperature, which is shown in table 3.
3) The tensile strengths of the modified polylactic acids and the raw material polylactic acid prepared in examples 1 to 6 and comparative examples 1 to 4 were measured: the results are shown in Table 3, performed according to the standard GB 1040-92.
TABLE 3
From the results in table 3, it can be seen that the impact strength of the polylactic acid composite materials of examples 1 to 6 is greater than that of the polylactic acid composite materials of comparative examples 1 to 4, which shows that the polylactic acid composite materials of examples 1 to 6 have good impact resistance, and the polylactic acid composite materials of examples 1 to 6 have excellent thermal stability and can maintain good biodegradability.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polylactic acid composite material is characterized by comprising the following raw materials in parts by mass: 100 parts of polylactic acid and 5-25 parts of elastomer;
the elastomer is mainly prepared by reacting and extruding polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide;
in the raw materials for preparing the elastomer, the feeding ratio of the polylactic acid to the acid lignin is 100 g: (8-20) g.
2. The polylactic acid composite material according to claim 1, wherein the polylactic acid is 100 parts by mass and the elastomer is 10 to 20 parts by mass in the raw materials for preparing the polylactic acid composite material.
3. The polylactic acid composite material according to claim 1, wherein the dicumyl peroxide is used in an amount of 0.5 to 1.5 wt% based on the total amount of the polylactic acid and the acid lignin in the raw material for preparing the elastomer.
4. The polylactic acid composite material according to claim 1, wherein the maleic anhydride is used in an amount of 1.5 to 4 wt% based on the total amount of the polylactic acid and the acid lignin in the raw material for preparing the elastomer.
5. The polylactic acid composite material as claimed in claim 1, wherein the raw material for preparing the elastomer has a ratio of polylactic acid to the acid lignin of 100 g: (10-18) g.
6. The polylactic acid composite material according to any one of claims 1 to 5, wherein the particle size of the elastomer is controlled in a range of less than 2mm by crushing.
7. The polylactic acid composite material according to any one of claims 1 to 5, wherein the acid lignin is obtained by extracting an acid from a straw.
8. A method for preparing a polylactic acid composite material according to any one of claims 1 to 7, comprising the steps of:
mixing polylactic acid, acid lignin, maleic anhydride and dicumyl peroxide to obtain a first premix;
reacting and extruding the first premix to prepare an elastomer;
mixing the elastomer and polylactic acid to obtain a second premix;
and melting and extruding the second premix to obtain the polylactic acid composite material.
9. The method according to claim 8, wherein the melt extrusion is performed using a screw extruder, wherein the temperature of the screw extruder is, in order of the material advancing direction: 120-145 ℃, 135-155 ℃, 145-165 ℃, 155-175 ℃, 165-180 ℃ and the head temperature is 160-170 ℃.
10. The method of claim 9, wherein the screw extruder is rotated at 90rpm to 120 rpm.
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| CN113308100A (en) * | 2021-07-09 | 2021-08-27 | 上海汉禾生物新材料科技有限公司 | Biodegradable polylactic acid/lignin composite material, preparation method and application |
| CN117903441A (en) * | 2024-03-19 | 2024-04-19 | 苏州禾润昌新材料有限公司 | Biodegradable polymer material and preparation method thereof |
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Application publication date: 20200331 |